WO1993001173A1 - Production of aromatic olefins - Google Patents
Production of aromatic olefins Download PDFInfo
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- WO1993001173A1 WO1993001173A1 PCT/US1992/005709 US9205709W WO9301173A1 WO 1993001173 A1 WO1993001173 A1 WO 1993001173A1 US 9205709 W US9205709 W US 9205709W WO 9301173 A1 WO9301173 A1 WO 9301173A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
- C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Definitions
- the present invention relates to a process for the direct production of aromatic olefins, starting with aryl chlorides.
- the process is based on the reaction of aryl chlorides with olefins and a base in the presence of a catalyst system comprising a palladium complex with a biphosphine ligand.
- Palladium-catalyzed vinylation of aryl halides is a known synthetic method for the production of aromatic olefins. Palladium catalyzed vinylation of aryl iodides and bromides has been described by T. Mizoroki, K. Mori and A. Ozaki, Bull Chem. Soc. Jpn. (1971) 4, 581 and by R.F. Heck and J.P. Nolley, Jr., J. Org. Chem. (1972) 37, 2320.
- European Patent No. 103544 discloses the reaction of chlorobenzenes with an olefin in the presence of a palladium catalyst, a base and an arsenic or phosphorous ligand. Yields up to 61% were obtained with substituted chlorobenzenes, but only 4% with unsubstituted chlorobenzene.
- European Patent Application EP 406 848 describes a process of catalytic formylation of aryl chlorides to produce aromatic aldehydes in the presence of a palladium complex of the formula [R ⁇ R_*-P(CH2)» ⁇ PR3R.4].*2Pd, wherein n is 3 or 4 and Ra. to R 4 are hydrogen, alkyl, cycloalkyl or aryl, at least one of them being alkyl or cycloalkyl.
- Ar is a radical selected from the group consisting of unsubstituted carbocyclic and heterocyclic aryl and carbocyclic and heterocyclic aryl substituted by one or more radicals selected from the group consisting of alkyl, carbocyclic aryl or aralkyl, fluoro, chloro, cyano, nitro, OR.*, S-alkyl, COR-*, CO2R- * and SO3R-*, wherein R 4 is hydrogen, alkyl, carbocyclic aryl or aralkyl; and Rx,R 2 ,R 3 are the same or different and each represent hydrogen, alkyl, carbocyclic aryl or aralkyl, chloro, fluoro, cyano, nitro, ORs, COaRs, CORs and wherein R s is hydrogen, alkyl, carbocyclic aryl or aralkyl, which comprises catalytic vinylation of an aryl chloride of the formula ArCl with an ary
- R s to Rs are selected from hydrogen, alkyl, cycloalkyl, unsubstituted carbocyclic aryl or aralkyl and carbocyclic aryl or aralkyl substituted by alkyl, alkoxy or phenoxy.
- alkyl as employed herein by itself or as part of another group includes both straight and branched chain radicals of up to 12 carbon atoms, preferably from 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl.
- carbocyclic aryl as employed herein by itself or as part of another group includes monocyclic or bicyclic Cs-Cxo aryl groups, such as phenyl and naphthyl, preferably phenyl.
- heterocyclic aryl as employed herein includes 5-6 membered heteroaromatic ring radicals containing one or more 0, S or N atoms, such as furyl, thienyl and pyridyl.
- cycloalkyl as employed herein includes saturated cyclic hydrocarbon groups containing from 3 to 7 carbon atoms, preferably cyclohexyl.
- the radical Ar is preferably phenyl optionally substituted by one or more radicals selected from the group consisting of alkyl, phenyl, fluoro, nitro, pyridyl, OR * ,
- R 4 is hydrogen, alkyl or phenyl.
- Rx and R** are preferably hydrogen or alkyl and R3 is preferably hydrogen, alkyl, COaR * , unsubstituted phenyl or phenyl substituted by alkyl or ORs, wherein Rs is hydrogen, alkyl or phenyl.
- R 3 to Rs are preferably alkyl, such as isopropyl, phenyl or cyclohexyl.
- the reaction takes place according to the following reaction scheme:
- the base used in the reaction may be an organic or inorganic base that is soluble, at least partially, in the reaction mixture. Suitable bases are exemplified by, but not limited to, sodium acetate, potassium acetate, potassium propionate, sodium carbonate and calcium carbonate.
- the reaction is advantageously carried out in a solvent that is inert to the reactants and products, preferably a polar solvent, such as dimethylformamide (DMF), dioxane, dimethylacetamide, sulfolane and N-methylpyrrolidone.
- the temperature of the reaction is generally between about 100- 250°C, the optimum temperature being about 150°C.
- the palladium compound used for the preparation of the palladium complex catalyst is any palladium salt or complex, such as palladium chloride, palladium acetate and palladium dibenzylideneacetone.
- the molar ratio of the palladium compound to the biphosphine is in the range of 1:0.5 to 1:100 Pd to biphosphine, the optimum being about 1:2.
- the palladium complex catalyst may be generated in situ under the catalytic reaction conditions from a palladium salt or complex and the biphosphine ligand.
- a palladium compound already containing the biphosphine ligand as part of its molecular structure may be utilized, in the presence or absence of additional biphosphine.
- suitable such complexes include Pd[(i-Pr)aP(CH 2 ) 4 P(i-Pr)a]a and
- the complex Pd[PhaP(CHa) 3 PPha]Cla is a precursor to the active catalyst and will be used in the presence of additional biphosphine.
- Example 1 Preparation of trans-4-benzoylstilbene.
- 2.17g of p-chlorobenzophenone were added, followed by 1.6g of sodium acetate and 1.3 g of styrene and the closed reaction vessel was heated under nitrogen and stirred at 150°C for 20 hrs.
- the reaction mixture was poured over a slurry of water and ice and the product was extracted with 800 ml of ether containing 20% methylene chloride. The organic layer was washed once with water and dried over anhydrous sodium sulfate.
- Example 2 Preparation of stilbene A solution containing 45 mg of palladium acetate and 116 mg of dippb in 4 ml of DMF was stirred at room temperature under nitrogen for 1 hr. 1.016 ml of chlorobenzene was added, followed by 1.3 ml of styrene and 840 mg of sodium acetate. The resulting mixture was heated and stirred in a closed vessel under nitrogen at 150°C for 24 hrs. After cooling to room temperature, the reaction mixture was poured over a water-ice slurry and extracted with ether containing 10% methylene chloride. The organic layer was separated and washed once with water, dried over anhydrous sodium sulfate and the solvent was removed under vacuum. The residue was purified on a silica column to give an 80% yield of trans-stilbene and 4.4% yield of cis-stilbene, characterized by X HNMR, IR and GC in comparison to authentic samples.
- Example 4 Preparation of trans-4-formyl-4'-methoxystilbene 4-Chlorobenzaldehyde was reacted with 4-methoxystyrene under the conditions of Example 1, to yield 1.9g(80% yield) of pure product.
- Aryl Chloride Olefin Product 4-chlorotoluene styrene 4-methylstilbene 3-chloroanisole styrene 3-methoxystilbene 4-chloroni robenzene styrene 4-nitrostilbene 4-fluorochlorobenzene styrene 4-fluorostilbene chlorobenzene 4-methoxy styrene 4-methoxystilbene chlorobenzene methyl acrylate methyl cinnamate 4-chlorobiphenyl methyl acrylate methyl 4-phenyl- cinnamate methyl 4-chloro- benzoate ethylene 4-carbomethoxy- styrene
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Abstract
Aromatic olefins are produced by catalytic vinylation of aryl chlorides in the presence of a base and of a palladium complex catalyst of the formula: [R6R7P(CH2)nPR8R9]2 Pd wherein n is 3 or 4 and R6 to R9 are selected from hydrogen, alkyl, cycloalkyl, unsubstituted carbocyclic aryl or aralkyl and carbocyclic aryl or aralkyl substituted by alkyl, alkoxy or phenoxy.
Description
PRODUCTION OF AROMATIC OLEFINS
FIELD OF THE INVENTION
The present invention relates to a process for the direct production of aromatic olefins, starting with aryl chlorides.
The process is based on the reaction of aryl chlorides with olefins and a base in the presence of a catalyst system comprising a palladium complex with a biphosphine ligand.
BACKGROUND OF THE INVENTION
Palladium-catalyzed vinylation of aryl halides, also known as the "Heck reaction", is a known synthetic method for the production of aromatic olefins. Palladium catalyzed vinylation of aryl iodides and bromides has been described by T. Mizoroki, K. Mori and A. Ozaki, Bull Chem. Soc. Jpn. (1971) 4, 581 and by R.F. Heck and J.P. Nolley, Jr., J. Org. Chem. (1972) 37, 2320.
A serious limitation of the Heck reaction is that aryl chlorides are usually unreactive. Various efforts to directly vinylate aryl chlorides have resulted in low yields and low catalyst stability.
A. Spencer, J. Organometal. Chem. (1984) 270, 115, reported vinylation of aryl chlorides catalyzed by palladium acetate in the presence of triphenylphosphine. Moderate yields of a maximum of 51% were obtained only when electron- withdrawing substituents were present on the aromatic ring. Chlorobenzene itself was essentially unreactive, leading to a poor 4% yield. In addition, only activated olefins were reported to undergo this reaction and a low catalyst turnover (a maXpiraum of 51) was obtained because of catalyst decomposition to unreactive palladium metal.
J.B. Davidson et. al., J. Mol. Catal. (1984) 22, 349, described vinylation of chlorobenzene with styrene to form stilbene catalyzed by palladium acetate in the presence of triphenylphosphine and water. Once again, only a moderate yield (a maximum of 56%) was obtained and the catalyst decomposed to palladium metal, resulting in a low catalyst turnover (maximum 25 turnover) . Benzene and biphenyl also formed in this reaction as undesirable by-products.
European Patent No. 103544 discloses the reaction of chlorobenzenes with an olefin in the presence of a palladium catalyst, a base and an arsenic or phosphorous ligand. Yields up to 61% were obtained with substituted chlorobenzenes, but only 4% with unsubstituted chlorobenzene.
United States Patent No. 4,814,489 and J.J. Bozell et al.,J. Am. Chem. Soc. (1988) 110, 2655, disclose the halide exchange reaction of aryl chlorides with iodide or bromide ions in the presence of a nickel catalyst to obtain aryl iodides or bromides, which are then reacted in a second reaction with an olefin in the presence of a palladium catalyst. However, stoichiometric amounts of the bromide or iodide salts are required. Also, the need to perform two separate reactions - the nickel catalyzed halide exchange reaction followed by the palladium vinylation reaction complicates the process. In addition, this process is completely ineffective in the presence of nitro substituents and the only exemplified olefins are ethyl acrylate and acrylonitrile.
European Patent Application EP 406 848 describes a process of catalytic formylation of aryl chlorides to produce aromatic aldehydes in the presence of a palladium complex of the formula [RιR_*-P(CH2)»χPR3R.4].*2Pd, wherein n is 3 or 4 and Ra. to R4 are hydrogen, alkyl, cycloalkyl or aryl, at least one of them being alkyl or cycloalkyl. DESCRIPTION OF THE INVENTION It has now been found according to the present invention that vinylation of aryl chlorides by reacting same with an
olefin and a base in the presence of a catalyst system comprising a palladium compound and a chelating biphosphine ligand leads to the production of aromatic olefins in high yields. The invention thus relates to a process for the production of aromatic olefins of the formula
[RβR-P(CHa)»PRβR93*2 Pd wherein n is 3 or 4 and Rs to Rs are selected from hydrogen, alkyl, cycloalkyl, unsubstituted carbocyclic aryl or aralkyl and carbocyclic aryl or aralkyl substituted by alkyl, alkoxy or phenoxy.
The term "alkyl" as employed herein by itself or as part of another group includes both straight and branched chain radicals of up to 12 carbon atoms, preferably from 1 to 8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl and isobutyl. The term "carbocyclic aryl" as employed herein
by itself or as part of another group includes monocyclic or bicyclic Cs-Cxo aryl groups, such as phenyl and naphthyl, preferably phenyl. The term "heterocyclic aryl" as employed herein includes 5-6 membered heteroaromatic ring radicals containing one or more 0, S or N atoms, such as furyl, thienyl and pyridyl. The term "cycloalkyl" as employed herein includes saturated cyclic hydrocarbon groups containing from 3 to 7 carbon atoms, preferably cyclohexyl.
The radical Ar is preferably phenyl optionally substituted by one or more radicals selected from the group consisting of alkyl, phenyl, fluoro, nitro, pyridyl, OR*,
C0R4 and C0aR4, wherein R4 is hydrogen, alkyl or phenyl.
Rx and R**. are preferably hydrogen or alkyl and R3 is preferably hydrogen, alkyl, COaR*, unsubstituted phenyl or phenyl substituted by alkyl or ORs, wherein Rs is hydrogen, alkyl or phenyl.
R3 to Rs are preferably alkyl, such as isopropyl, phenyl or cyclohexyl. The reaction takes place according to the following reaction scheme:
Among the biphosphine ligands of the type
RβR*7P(CH2)nPR8Rs, used to prepare the complex catalyst, the prefered compounds are:
(i-Pr)2P(CHa)3P(i-Pr)a(dippp) ; Cy2P(CHa)*PPha;
(i-Pr)aP(CHa)4P(i-Pr)a(dippb); CyaP(CH2)3PCya;
PhaP(CHa)3PPha(dppp); wherein i-Pr - isopropyl; Ph = phenyl; Cy = cyclohexyl. The molar ratio of the palladium compound to the biphosphine is in the range of 1:0.5 to 1:100 Pd to biphosphine, the optimum being about 1:2.
The palladium complex catalyst may be generated in situ under the catalytic reaction conditions from a palladium salt or complex and the biphosphine ligand. Alternatively, a palladium compound already containing the biphosphine ligand as part of its molecular structure may be utilized, in the presence or absence of additional biphosphine. Examples for suitable such complexes include Pd[(i-Pr)aP(CH2)4P(i-Pr)a]a and
Pd[PhaP(CHa)3PPha]a.
The complex Pd[PhaP(CHa)3PPha]Cla is a precursor to the active catalyst and will be used in the presence of additional biphosphine.
The invention will now be illustrated by the following non-limiting examples.
Example 1. Preparation of trans-4-benzoylstilbene. A solution containing 23 mg of palladium acetate and 58 mg of dippb in 5 ml of DMF was stirred at room temperature under nitrogen for 1 hr. 2.17g of p-chlorobenzophenone were added, followed by 1.6g of sodium acetate and 1.3 g of styrene and the closed reaction vessel was heated under nitrogen and stirred at 150°C for 20 hrs. The reaction mixture was poured over a slurry of water and ice and the
product was extracted with 800 ml of ether containing 20% methylene chloride. The organic layer was washed once with water and dried over anhydrous sodium sulfate. The solvent was removed under vacuum to yield a solid residue which was washed with pentane containing 20% of ether. 2.556g (90% yield) of pure crystalline trans-4-benzoylstilbene were obtained, characterized by IR,1H-NMR and MS.
Example 2. Preparation of stilbene A solution containing 45 mg of palladium acetate and 116 mg of dippb in 4 ml of DMF was stirred at room temperature under nitrogen for 1 hr. 1.016 ml of chlorobenzene was added, followed by 1.3 ml of styrene and 840 mg of sodium acetate. The resulting mixture was heated and stirred in a closed vessel under nitrogen at 150°C for 24 hrs. After cooling to room temperature, the reaction mixture was poured over a water-ice slurry and extracted with ether containing 10% methylene chloride. The organic layer was separated and washed once with water, dried over anhydrous sodium sulfate and the solvent was removed under vacuum. The residue was purified on a silica column to give an 80% yield of trans-stilbene and 4.4% yield of cis-stilbene, characterized by XHNMR, IR and GC in comparison to authentic samples.
Example 3. Preparation of trans-4-benzoyl-4'-methoxystilbene
4-Chlorobenzophenone was reacted with 4-methoxystyrene under the same conditions of Example 1, except for using ether containing 30% of methylene chloride to completely dissolve the product. 2.897g (92.3% yield) of pure crystalline trans-4-benzoyl-4'-methoxystilbene was obtained, characterized by IR, XH-NMR and MS.
Example 4. Preparation of trans-4-formyl-4'-methoxystilbene 4-Chlorobenzaldehyde was reacted with 4-methoxystyrene under the conditions of Example 1, to yield 1.9g(80% yield)
of pure product.
Example 5. Preparation of styrene
A solution containing 45 mg of palladium acetate and 165 mg of dppp in 10 ml of DMF was stirred for 1 hr at room temperature under nitrogen in a 500 ml glass pressure vessel.
2.12 g of sodium carbonate and 1.016 ml of chlorobenzene were added, followed by addition of ethylene to a pressure of 20 psi. The reaction mixture was heated at 140°C for 24 hrs, after which it was cooled to room temperature and the gas was vented off. GC analysis of the reaction mixture showed formation of styrene in 70% yield.
Using other starting materials, the following products were produced according to the process of the present invention:
Aryl Chloride Olefin Product 4-chlorotoluene styrene 4-methylstilbene 3-chloroanisole styrene 3-methoxystilbene 4-chloroni robenzene styrene 4-nitrostilbene 4-fluorochlorobenzene styrene 4-fluorostilbene chlorobenzene 4-methoxy styrene 4-methoxystilbene chlorobenzene methyl acrylate methyl cinnamate 4-chlorobiphenyl methyl acrylate methyl 4-phenyl- cinnamate methyl 4-chloro- benzoate ethylene 4-carbomethoxy- styrene
3-chloropyridine styrene β-(3-pyridyl)- styrene
The invention will now be defined by the following non- limiting claims.
Claims
1. A process for the production of an aromatic olefin of the formula 
wherein
Ar is a radical selected from the group consisting of unsubstituted carbocyclic and heterocyclic aryl and carbocyclic and heterocyclic aryl substituted by one or more radicals selected from the group consisting of alkyl, carbocyclic aryl or aralkyl, fluoro, chloro, cyano, nitro, 0R4, S-alkyl, COR4, C0aR4 and S03R4, wherein R4 is hydrogen, alkyl, carbocyclic aryl or aralkyl; and Rx,Ra,R3 are the same or different and each represent hydrogen, alkyl, carbocyclic aryl or aralkyl, chloro, fluoro, cyano, nitro, ORs, COaRs, CORs and (Rx)C=C(Ra)R3, wherein Rs is hydrogen, alkyl, carbocyclic aryl or aralkyl, which comprises catalytic vinylation of an aryl chloride of the formula ArCl with an olefinic compound of the formula 
wherein Ar, Rx, R2 and R3 are as defined above, in the presence of a base and of a palladium complex catalyst of the formula:
[RsR-7P(CH2),*.PReR.--.]a Pd wherein n is 3 or 4 and R6 to R9 are selected from hydrogen, alkyl, cycloalkyl, unsubstituted carbocyclic aryl or aralkyl and carbocyclic aryl or aralkyl substituted by alkyl, alkoxy or phenoxy.
2. A process according to claim 1 wherein the palladium complex catalyst is generated in situ by reaction of a palladium salt or complex with a biphosphine ligand of the formula RsR? (CHa)ΛPRβRs, wherein n and R6 to Rs are as defined in Claim 1.
3. A process according to claim 2 wherein the palladium salt is palladium acetate.
4. A process according to claim 1 wherein R6 to Rs are isopropyl and n is 3 or 4.
5. A process according to claim 1 wherein R6 and R7 are cyclohexyl and Rβ and R are phenyl and n is 4.
6. A process according to claim 1 wherein Re to Rs are phenyl and n is 3.
7. A process according to claim 1 wherein R6 to Rs are cyclohexyl and n is 3.
8. A process according to claim 1 or 2 wherein Ar is unsubstituted phenyl or phenyl substituted by allcyl, phenyl, pyridyl, nitro, fluoro, OR4, C0R4 and COaR«, wherein R4 is hydrogen, alkyl or phenyl, Rx and Ra are hydrogen and R3 is unsubstituted phenyl or phenyl substituted by ORs, wherein Rs is alkyl.
9. A process according to clai 1 or 2 wherein Ar is unsubstituted phenyl or phenyl substituted by phenyl or COOCHs, R and R2 are hydrogen and R3 is hydrogen or COOCH3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL98781 | 1991-07-10 | ||
| IL98781A IL98781A0 (en) | 1991-07-10 | 1991-07-10 | Process for the production of aromatic olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993001173A1 true WO1993001173A1 (en) | 1993-01-21 |
Family
ID=11062625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1992/005709 WO1993001173A1 (en) | 1991-07-10 | 1992-07-07 | Production of aromatic olefins |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2377292A (en) |
| IL (1) | IL98781A0 (en) |
| WO (1) | WO1993001173A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0597291A1 (en) * | 1992-10-23 | 1994-05-18 | Nihon Iyakuhin Kogyo Co., Ltd. | 2,3-diphenyl-5-pyrrolyl-furan derivatives, processes and intermediates for their preparation and their use as anti-inflammatory, and anti-allergic and platelet aggregation inhibiting agents |
| EP0719758A1 (en) * | 1994-12-29 | 1996-07-03 | Hoechst Aktiengesellschaft | Process for the production of aromatic olefines |
| WO1996025376A1 (en) * | 1995-02-17 | 1996-08-22 | Albemarle Corporation | Process for preparing olefins |
| EP1437347A2 (en) * | 2003-01-07 | 2004-07-14 | Bayer Chemicals AG | Process for the preparation of arylvinyl halides and aralkinyl compounds |
| US20120330052A1 (en) * | 2010-03-23 | 2012-12-27 | Canon Kabushiki Kaisha | Conjugated aromatic compound, optical material, and optical element |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4736057A (en) * | 1983-11-11 | 1988-04-05 | Imperial Chemical Industries Plc | Cyclohexane derivatives |
| US4814489A (en) * | 1987-07-24 | 1989-03-21 | Monsanto Company | Process for the preparation of substituted olefins from unsaturated organic chlorides and olefins |
| EP0406848A1 (en) * | 1989-07-05 | 1991-01-09 | Yeda Research And Development Company Limited | Production of aromatic aldehydes |
-
1991
- 1991-07-10 IL IL98781A patent/IL98781A0/en unknown
-
1992
- 1992-07-07 WO PCT/US1992/005709 patent/WO1993001173A1/en active Application Filing
- 1992-07-07 AU AU23772/92A patent/AU2377292A/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4736057A (en) * | 1983-11-11 | 1988-04-05 | Imperial Chemical Industries Plc | Cyclohexane derivatives |
| US4814489A (en) * | 1987-07-24 | 1989-03-21 | Monsanto Company | Process for the preparation of substituted olefins from unsaturated organic chlorides and olefins |
| EP0406848A1 (en) * | 1989-07-05 | 1991-01-09 | Yeda Research And Development Company Limited | Production of aromatic aldehydes |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0597291A1 (en) * | 1992-10-23 | 1994-05-18 | Nihon Iyakuhin Kogyo Co., Ltd. | 2,3-diphenyl-5-pyrrolyl-furan derivatives, processes and intermediates for their preparation and their use as anti-inflammatory, and anti-allergic and platelet aggregation inhibiting agents |
| EP0719758A1 (en) * | 1994-12-29 | 1996-07-03 | Hoechst Aktiengesellschaft | Process for the production of aromatic olefines |
| CN1075050C (en) * | 1994-12-29 | 2001-11-21 | 塞拉尼斯有限公司 | Process for preparing atomatic olefins |
| WO1996025376A1 (en) * | 1995-02-17 | 1996-08-22 | Albemarle Corporation | Process for preparing olefins |
| EP1437347A2 (en) * | 2003-01-07 | 2004-07-14 | Bayer Chemicals AG | Process for the preparation of arylvinyl halides and aralkinyl compounds |
| JP2004210788A (en) * | 2003-01-07 | 2004-07-29 | Bayer Chemicals Ag | Method for producing arylvinyl halide or sulfonate and arylalkyne and compounds produced thereby |
| EP1437347A3 (en) * | 2003-01-07 | 2004-09-22 | Bayer Chemicals AG | Process for the preparation of arylvinyl halides and aralkinyl compounds |
| US7312350B2 (en) | 2003-01-07 | 2007-12-25 | Lanxess Deutschland Gmbh | Process for preparing arylalkynes |
| US20120330052A1 (en) * | 2010-03-23 | 2012-12-27 | Canon Kabushiki Kaisha | Conjugated aromatic compound, optical material, and optical element |
| US9176257B2 (en) * | 2010-03-23 | 2015-11-03 | Canon Kabushiki Kaisha | Conjugated aromatic compound, optical material, and optical element |
Also Published As
| Publication number | Publication date |
|---|---|
| IL98781A0 (en) | 1992-07-15 |
| AU2377292A (en) | 1993-02-11 |
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